Alkenylaryloxyacetamides



materials. That is, 2,3,4,5

United States Patent F ALKENYLARYLOXYACETAMIDES Gaetano F. DAlelio', Pittsburgh, Pa., assignor to Koppers Company, Inc., a corporation of Delaware No Drawing. Application October 20, 1954, Serial No. 463,610

30 Claims. (Cl. 260-47) This application is concerned with certain new alkenylaryloxyacetamides. It is concerned with these substances in their monomeric as well as polymeric form.

Further, the invention is concerned with insoluble or cured polymers which can be obtained by aftertreating polymeric alkenylaryloxyacetamides to cause crosslinking.

This invention is particularly concerned with alkenylaryloxyacetamides of the formula R ll oH=dAr0-0HzGNR', in which R is chosen from the class consisting of hydrogen and methyl, Ar is an arylene radical and R is chosen from the class consisting of hydrogen, alkyl, aryl, aralkyl, alkaryl and in which R can be linked with nitrogen to form a hetrocyclic group of the formula {-R' which represents a heterocyclic ring having less than 7 carbon atoms such as for example the groups pyridyl, pyrimidyl, amino-1,2,4-triazolyl, piperidyl, piperazino, and morpholino. In the foregoing formula R when alkyl can be represented by such radicals as for example, methyl, ethyl, propyl, n-butyl, sec-butyl, amyl, hexyl, decyl and the like; when R is aryl it can be illustrated by such radicals as, for example, phenyl naphthyl, chlorophenyl and the like; when R is aralkyl it can be, for example, such radicals as benzyl, 3-phenylpropyl; and when alkaryl, such radicals as, for example, tolyl, xylyl, ethylphenyl and the like.

In particular the invention is concerned with alkenylaryloxyacetamides, particularly vinyland isopropenylphenoxyacetamides. These polymers are useful in many polymer applications such as, for example, for post-reaction with cross-linking agents such as polyisocyanates, polyoxiranes, and formaldehyde in those instances in which at least one R is hydrogen.

As used herein the term polymer embraces both homopolymers and copolymers. The term copolymer as used herein embraces polymeric materials derived from the polymerization of two or more monomeric ad infinitum copolymerizable monomeric substances can be copolymerized to produce a copolymer. As used herein the terms parts and percentages indicate parts and percentages by weight unless otherwise specified. The invention is illustrated by, but not restricted to, the following preferred embodiments:

Example I a Dean-Stark type trap and with means for introduction of a gas below the surface of the toluene solution. Am-

- monia is bubbled into and through the solution while it is heated to and maintained at reflux temperature. The

- refluxing and addition of ammonia is continued until the theoretical quantity of water is collected, that is approximately 10 parts water.

2,811,507 Patented Oct. 29, 1957 carbon, hydrogen and nitrogen and by hydrogen absorption, the results of which are in substantial agreement with the theoretical values.

Exqmplell The procedure of Example I is repeated substituting for the 2-vinylphenoxyacetic acid there used a similar quantity of 4-isopropenylphenoxyacetic acid. There is obtained 4-isopropenyl-phenoxyacetamide, which is characterized by analyses for carbon, hydrogen and nitrogen and by hydrogen absorption, the results of which are in substantial agreement with the theoretical values.

It will be realized that in Examples I and II for the 2- vinylphenoxyacetic acid and 4-isopropenylphenoxyacetic acid there used, there can be substituted equimolar quantities of alkenylaryloxyacetic acid illustrated by such com pounds as, for example, v.:-vinylphenoxyacetic acid; 4- vinylphenoxyacetic acid; 3-isopropenylphenoxyacetic acid; the vinyland isopropenyl-land -2-naphthols and the like.

Additionally, amines of the formula HNRz in which R has the meaning heretofore described can be utilized in place of ammonia. In those instances in which the amines are liquid or solid an equimolar quantity of amine based on the acid is utilized and refluxing is continued until the theoretical amount of water is evolved.

Illustrative of the amines which can be utilized are such compounds as methylamine, ethylamine, propylamine, butylamine, decylamine, dimethylamine, dipropylamine, dibutylamine, didecylamine, aniline, methylaniline, propylaniline, benzylamine, dibenzylamine, dimethylaminoanilines, the aminopyridines, the aminopyrimidines, guanazole and the like. There are obtained the various alkenylaryloxyacetamides of this invention. These monomeric compounds of this invention are characterized by carbon, hydrogen and nitrogen analyses and by hydrogen absorption which give results which are in substantial agreement with the theoretical values.

Example 111 Ten parts 2-vinylphenoxyacetamide (obtained as in Example I) are dissolved in parts xylene and there is added 0.5 percent benzoyl peroxide based on the acetamide. The mixture is cooled to the temperature of a Dry Ice bath and atmosphere alternately evacuated and filled with nitrogen. Polymerization is carried out under an atmosphere of nitrogen at approximately C. for one day. The xylene is removed by vacuum distillation. Thgre is obtained homopolymeric 2-vinylphenoxyacetam1 e.

Example IV Example III is repeated substituting for the 2-vinylphenoxyacetamide there used a similar quantity of 4- isopropenylphenoxyacetamide (obtained as in Example II). There is obtained homopolymeric 4-isopropenylphenoxyacetamide.

Similarly, the various homopolymers of this invention are obtained following the procedure set forth in Example III and substituting for the Z-Vinylphenoxyacetamide there used similar quantities of various alkenylaryloxy acetamides of this invention as illustrated by the structural formula in which R, R' and Ar have the meanings heretofore described. Further, the homopolymers of this invention as, for example, fibers.

Example V Two hundred parts of homopolymeric 2-viny1phen0xyacetic acid obtained as described in Example I of my copending application filed concurrently herewith are dissolved in 2000 parts toluene and treated with 140 parts thionyl chloride at reflux temperature to produce the acid 7 chloride form of polymer. The unreacted thionyl chloride is removed by distillation in a vacuum.

The residue is maintained at reflux and ammonia is introduced beneath the surface of the toluene uutilahsorption of ammonia ceases. The toluene is removed by vacuum distillation and there is obtained homopolymen'c 2vinylphenoxyacetamide.

It will be realized that in the foregoing example there can be substituted for the .homopolymeric 2-vinylphenoxyacetic acid similar quantities of homopolymeric alkenylaryloxyacetic acids such as for example homopolymeric 4-isopropenylphenoxyacetic acid, obtained as described in my above-referred to copending application. Similarly, for the ammonia utilized in this example there can be substituted various amines of the general formula HNR'z in which R has the meaning heretofore described.

Example VI Ten parts 2-vinylphenoxyacetamide (obtained as described in Example I), 90 parts styrene and 0.5 part ben- I Example VII Example VI is repeated substituting for the styrene there used a similar quantity of butadiene. There is obtained a copolymer soluble in toluene.

Example VIII Example VI is repeated substituting for the styrene there used a similar quantity of acrylonitrile. There is obtained a polymer soluble is dimethylformamide.

It is to be noted that this coplolymer can be cold drawn to produce molecularly oriented shaped articles such It is further to be noted that these copolymers possess dye-receptivity .as compared to acrylom'trile polymers. That is, when polymeric acrylonitrile and the subject copolymer are subjected to thesame dye treatment the latter is deeply dyed, whereas the former is dyed only slightly.

Example IX Example VI is repeated substituting for the styrene therein used a similar quantity of maleic anhydride. There is obtained a polymer soluble in toluene.

Example X Example VI is repeated substituting for the styrene there used a similar quantity of methyl methacrylate. There is obtained a polymer soluble in toluene.

Example XI Example VI is repeated substituting for the 2-vinylphenoxyacetamide there used a'similar quantity of--4-isopropenylphenoxyacetamide (obtained as in Example II). There is obtained a linear soluble copoly'mer. Similarly, the various alkenylaryloxyacetamides of this invention can be utilized in place of 4-isopropenylphenoxyacctamide used herein. Additionally, it will be realized that ---the various other ethylenically unsaturated monomers utilized in the -Examples Ylthrough'X inclusive can be 4,4 xenylenediisocyanate;

utilized herein in combination with the alkenylaryloxyacetamides to yield copolymers. Further, there can be utilized mixtures of two or more alkenylaryloxy acetamides in the preparation of copolymers either alone or in combination with a copolym'erizable ethylenically unsaturated monomer or mixtures of two or more copolymerizable ethylenically unsaturated monomers.

It is tobe noted that for benzoyl peroxide utilized in the foregoing examples there can be substituted a variety of peroxy-catalysts such as hydrogen, acetyl, acety1-ben. zoyl, phthalyl and lauroyl peroxides, tertiary-butyl hydroperoxides, etc., and, other per QQmPounds, for example ammonium persulfate, sodium persulfate, sodium perchlorate and the like.

Example XII One hundred parts of the polymer of Example III is admixed with 10 parts of diglycidyl ether of bisphenol and 1 percent of ethylene diamine and the mixture warmed gently. There is obtained a thermoset resin.

Example XIII Example XII is repeated utilizing in place of diglycidyl ether of bisphenol an equal weight of the resin described at column 7 of my U. S. Patent 2,658,885, granted'November 10, 1953. There is obtained -a thermoset resin.

It will be realized that the various epoxyalkoxy hydrocarbon substituted phenol aldehyde resins described in that patent can be utilized in the foregoing procedure. Additionally the epoxyalkoxy chloro-substituted phenol aldehyde resins described in my U. S. Patent 2,658,884, granted November 10, 1953, can be utilized in the toregoing procedure.

It will be understood that in place of the ethylenediamine catalyst utilized in Examples XLI and XIII there can be substituted equivalent portions of such amine catalysts as tetrahydroquinoline andpiperidine to pbtain substantially similar results.

There can be substituted for the polymer utilized in Examples XII and XIII similar quantities of the various polymers of this invention, that is, polymers of alkenylaryloxy acetamides.

Example XIV One hundred parts of the copolymer of Example NI is admixed with approximately 10 parts 12,4-tolufinediisocyanate and the mixture warmed. There is obtained a thermoset resin.

In place of the 2,4 toluenediisocyanate utilized above there can be substituted otherdiisocyanates such as phenylenediisocyanate; 2,6-toluenediisocyanate; l ,5-naphthalenediisocyanate; l-chloro-l-phenylene-2,4rdiisocyanate; tetramethylenediisocyanate and the like. The amount of these diisocyanatesutilized is governed by the degree of .crosselinkingdesired.

Example XV One hundred parts of the polymer of Example III are. intimately admixed with, approximately 15 parts hexamethylenetetramine and the mixture cured in ,a; n1old according to conventional techniques. A thermoset resin results.

Example XVI One hundred parts of the polymer of Example ;III are intimately admixed with approximately 10 parts hexamethylenetetramine and 5 parts urea and the mixture cured in a mold according to conventional techniques. A thermoset resin results.

It will be realized that such aldehyde rcactivenitrggpn containing substances as, for example, .melarnine, can be substituted .in the foregoing for the urea {to pbtain substantially similar results.

As used herein the'term aryl embraces a yarietyof I aromatic nucIe-isuch as phenyl, naphthyl, andihezlQwer allgyl and halogen substituted nuclei, that isthe aryl 111.11-

clei containing one or more methyl, ethyl, propyl, butyl,

CH2=( 3AIOCH2 -NR'2 in which R is chosen from the class consisting of hydrogen and methyl, Ar is an arylene radical, and R is chosen.

from the class consisting of hydrogen, alkyl, aryl, aralkyl and alkaryl and in which R can be linked with nitrogen to form a heterocyclic group of the formula (-R' which represents a heterocyclic ring having less than 7 carbon atoms.

2. 2-vinylphenoxyacetamide.

3. 4-isopropenylphenoxyacetamide.

4. 3-vinylphenoxyacetamide.

5. 4-vinylphenoxyacetamide.

6. 3-isopropenylphenoxyacetamide.

7. A homopolymer of an alkenylaryloxyacetamide of claim 1.

8. A polymer of an alkenylaryloxyacetamide having a plurality of repeating units of the formula in which R is chosen from the class consisting of hydrogen and methyl, Ar is an arylene radical, and R is chosen from the class consisting of hydrogen, alkyl, aryl, aralkyl and alkaryl and in which R can be linked with nitrogen to form a heterocyclic group of the formula {R which represents a heterocyclic ring having less than 7 carbon atoms.

9. A copolymer of an alkenylaryloxyacetamide of claim 1 and at least one other copolymerizable ethylenically unsaturated monomer.

10. A copolymer of 2-vinylphenoxyacetamide and at least one other copolymerizable ethylenically unsaturated monomer.

11. A copolymer of claim 9 in which the unsaturated monomer is styrene.

12. A copolymer of claim 9 in which the unsaturated monomer is acrylonitrile.

13. A copolymer of claim 9 in which the unsaturated monomer is butadiene.

14. A copolymer of claim 9 in which the unsaturated monomer is maleic anhydride.

15. A copolymer of claim 9 in which the unsaturated monomer is methyl methacrylate.

16. An insoluble polymer of a polymerizable mass comprising an alkenylaryloxyacetamide of claim 1 and at least one other polymerizable ethylenically unsaturated monomer, said polymer being cross-linked by a plurality of linkages derived from said amide groups.

17. An insoluble polymer of a polymerizable mass comprising at least one other polymerizable ethylenically unsaturated monomer and 2-vinylphenoxyacetamide, said polymer being cross-linked by a plurality of linkages derived from said amide group.

18. A polymer of claim 16 in which the unsaturated monomer is styrene.

19. A polymer of claim 16 in which the unsaturated monomer is acrylonitrile.

20. A polymer of claim 16 in which the unsaturated monomer is butadiene.

2l. A polymer of claim 16 in which the unsaturated monomer is maleic anhydride.

22. A polymer of claim 16 in which the unsaturated monomer is methyl methacrylate.

23. A copolymer of 4-isopropenylphenoxyacetamide and at least one other copolymerizable ethylenically unsaturated monomer.

24. A copolymer of 3-vinylphenoxyacetamide and at least one other copolymerizable ethylenically unsaturated monomer.

25. A copolymer of 4-vinylphenoxyacetamide and at least one other copolymerizable ethylenically unsaturated monomer.

26. A copolymer of 3-isopropenylphenoxyacetamide and at least one other copolymerizable ethylenically unsaturated monomer.

27. An insoluble polymer of a polymerizable mass comprising 4-isopropenylphenoxyacetamide and at least one otherpolymerizable ethylenically unsaturated monomer, said polymer being cross-linked by a plurality of linkages derived from said amide group.

28. An insoluble polymer of a polymerizable mass comprising 3-vinylphenoxyacetamide and at least one other polymerizable ethylenically unsaturated monomer, said polymer being cross-linked by a plurality of linkages derived from said amide group.

29. An insoluble polymer of a polymerizable mass comprising 4-vinylphenoxyacetamide and at least one other polymerizable ethylenically unsaturated monomer, said polymer being cross-linked by a plurality of linkages derived from said amide group.

30. An insoluble polymer of a polymerizable mass comprising 3-isopropenylphenoxyacetamide and at least one other polymerizable ethylenically unsaturated monomer, said polymer being cross-linked by a plurality of linkages derived from said amide group.

References Cited in the file of this patent UNITED STATES PATENTS 543,579 Lederer July 30, 1895 2,181,119 Caplan Nov. 28, 1939 2,343,547 Gordon Mar. 7, 1944 FOREIGN PATENTS 65,393 Germany Oct. 27, 1892 OTHER REFERENCES Newman et al.: Jour. Amer. Chem. Soc., vol. 69, 1947, pp. 718, 720, 722, and 723. (Copy in Sci. Lib.) 

8. A POLYMER OF AN ALKENYLARYLOXYACETAMIDE HAVING A PLURALITY OF REPEATING UNITS OF THE FORMULA 